CN111057018A - Method for producing 2-(2'-hydroxy-3'-methyl-5'-carboxyphenyl)benzotriazole - Google Patents
Method for producing 2-(2'-hydroxy-3'-methyl-5'-carboxyphenyl)benzotriazole Download PDFInfo
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- NDHICDVRYHYFDQ-UHFFFAOYSA-N OC1=C(C=C(C=C1C)C(=O)O)N1N=C2C(=N1)C=CC=C2 Chemical compound OC1=C(C=C(C=C1C)C(=O)O)N1N=C2C(=N1)C=CC=C2 NDHICDVRYHYFDQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- -1 alkali metal nitrite Chemical class 0.000 claims abstract description 43
- 239000012954 diazonium Substances 0.000 claims abstract description 31
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 31
- LTFHNKUKQYVHDX-UHFFFAOYSA-N 4-hydroxy-3-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1O LTFHNKUKQYVHDX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims description 7
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000004304 potassium nitrite Substances 0.000 claims description 6
- 235000010289 potassium nitrite Nutrition 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 claims description 3
- 229960003868 paraldehyde Drugs 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 abstract description 13
- 230000002745 absorbent Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 6
- 230000000903 blocking effect Effects 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 239000005022 packaging material Substances 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 32
- 238000006722 reduction reaction Methods 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 12
- 239000012964 benzotriazole Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention is a method for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole. The method comprises the following steps: a. reacting o-nitroaniline with alkali metal nitrite under the conditions of inorganic strong acid and low temperature to synthesize diazonium salt; b. under the alkaline condition, 3-methyl-4-hydroxy-benzoic acid is dissolved in aliphatic solvent and coupled with diazonium salt under the low temperature condition to obtain azo compound; c. the azo compound is used for producing a semi-reduction product under the action of a reducing agent under the alkaline condition; d. the semi-reduction product is put in organic solvent and under the action of metal reducing agent, so that the product is obtained. The ultraviolet absorbent can effectively absorb ultraviolet light of 270-340 nm, and can be widely applied to PE, PVC, PP, PS, PC, polypropylene fiber, ABS resin, epoxy resin, resin fiber, ethylene vinyl acetate and the like. And can be used for packaging materials such as plastic containers, food packaging boxes and the like, and has good light stabilization effect. The ultraviolet absorbent has high ultraviolet absorptivity and high blocking rate, is not easy to leach, and has good effect.
Description
Technical Field
The invention relates to a method for preparing benzotriazole ultraviolet absorbent, in particular to a method for preparing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole.
Background
Uv absorbers are the main type of light stabilizers and are a class of substances that are strongly selective for absorbing high energy uv light and performing energy conversion, releasing or dissipating energy in the form of thermal energy or harmless low radiation. The existing ultraviolet absorbent mainly comprises benzophenone absorbent, carboxylic acid absorbent and benzotriazole absorbent. The benzophenone absorbent and the carboxylic acid absorbent have low ultraviolet absorptivity, low barrier rate, easy leaching and short service life of protected materials (such as plastics). The benzotriazole absorbent has the advantages of wide ultraviolet absorption wavelength range, oil resistance, discoloration resistance, low volatility, low toxicity and good compatibility with polymers.
A new benzotriazole ultraviolet absorber with high absorptivity, high rejection rate and difficult leaching is needed to realize industrial application.
Disclosure of Invention
The invention aims to provide a method for preparing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole, which has high absorption rate and high barrier rate and is difficult to leach out.
The technical scheme of the invention is as follows:
a process for the manufacture of 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole comprising the steps of:
a. reacting o-nitroaniline with alkali metal nitrite under the conditions of inorganic strong acid and low temperature to synthesize diazonium salt;
b. under the alkaline condition, 3-methyl-4-hydroxy-benzoic acid is dissolved in aliphatic solvent and coupled with diazonium salt under the low temperature condition to obtain azo compound;
c. the azo compound is used for producing a semi-reduction product under the action of a reducing agent under the alkaline condition;
d. the semi-reduction product is put in organic solvent and under the action of metal reducing agent, so that the product is obtained.
The strong inorganic acid used is hydrochloric acid or sulfuric acid.
The reaction temperature in the a.b step is controlled below 5 ℃.
The alkali metal nitrite used includes sodium nitrite or potassium nitrite.
The alkaline condition is that a certain amount of NaOH, KOH or Ca (OH) is added into a solvent2And (4) forming.
The aliphatic solvent comprises cyclohexane, octane and petroleum ether.
The reducing agent comprises inorganic salts: na (Na)2S、NaHS、NH4HS、(NH4)2S and their mixture, the aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, paraldehyde, reducing sugar, and hydrazine.
The metal reducing agent comprises Zn, Sn, Al, Fe and a mixture thereof.
The organic solvent comprises dimethylbenzene, methylbenzene and benzene.
The molar ratio of the o-nitroaniline to the 3-methyl-4-hydroxy-benzoic acid is 1: 1; the mass ratio of the alkali metal nitrite to the o-nitroaniline is 5-6: 10.
the invention has the beneficial effects that:
1. the ultraviolet absorbent can effectively absorb ultraviolet light of 270-340 nm, and can be widely applied to PE, PVC, PP, PS, PC, polypropylene fiber, ABS resin, epoxy resin, resin fiber, ethylene vinyl acetate and the like. And can be used for packaging materials such as plastic containers, food packaging boxes and the like, and has good light stabilization effect.
2. The ultraviolet absorbent has high ultraviolet absorptivity and high blocking rate, is not easy to leach, and has good effect.
Drawings
FIG. 1 shows an ultraviolet absorption spectrum of 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole in preparation.
Detailed Description
A process for the manufacture of 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole comprising the steps of:
a. reacting o-nitroaniline with alkali metal nitrite under the conditions of inorganic strong acid and low temperature to synthesize diazonium salt;
b. under the alkaline condition, 3-methyl-4-hydroxy-benzoic acid is dissolved in aliphatic solvent and coupled with diazonium salt under the low temperature condition to obtain azo compound;
c. the azo compound is used for producing a semi-reduction product under the action of a reducing agent under the alkaline condition;
d. the semi-reduction product is put in organic solvent and under the action of metal reducing agent, so that the product is obtained.
The strong inorganic acid used is hydrochloric acid or sulfuric acid. The reaction temperature in the a.b step was controlled to 5 ℃ or lower. The alkali metal nitrite used includes sodium nitrite or potassium nitrite. The alkaline conditions described are the addition of an amount of NaOH, KOH or Ca (OH) to the solvent2And (4) forming. Aliphatic solvents mentioned include cyclohexane, octane, petroleum ether. Reducing agents described include inorganic salts: na (Na)2S、NaHS、NH4HS、(NH4)2S and their mixture, the aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, paraldehyde, reducing sugar, and hydrazine. Metallic reducing agents are described as Zn, Sn, Al, Fe and mixtures thereof. The organic solvents mentioned are xylene, toluene, benzene.
Examples
1. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 28ml of hydrochloric acid (33%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 0 ℃, adding 5.5g of sodium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: 100ml of cyclohexane and 13g of 3-methyl-4-hydroxy-benzoic acid are added into a 500ml three-necked flask provided with a stirrer and a thermometer, and after stirring and dissolving at room temperature, NaOH10g is added, stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into the three-necked flask within 0.5 hour. 25g of a red azo compound was obtained.
c, half reduction reaction: in that1000ml three-necked flask equipped with a stirrer and a thermometer were charged with the above azo compound, Ca (OH)210g，NH4HS20g, and deionized water 280 ml. Stirring, heating to 50 ℃, reacting for 1 hour to obtain 23g of yellow semi-reduction product.
d, reduction reaction: 23g of semi-reduction product, 300ml of benzene and 15g of Fe powder are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, stirred and heated to 60 ℃, and reacted for 1 hour to obtain 18g of white product with the content of 99.1 percent.
2. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 6ml of sulfuric acid (93%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 5 ℃, adding 5g of potassium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: 100ml of cyclohexane and 13g of 3-methyl-4-hydroxy-benzoic acid are added into a 500ml three-necked flask provided with a stirrer and a thermometer, and after stirring and dissolving at room temperature, NaOH10g is added, stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into the three-necked flask within 0.5 hour. 25g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer were charged the above azo compound, Ca (OH)210g, reducing sugar 20g and deionized water 280 ml. Stirring, heating to 50 ℃, reacting for 1 hour to obtain 23g of yellow semi-reduction product.
d, reduction reaction: 23g of semi-reduction product, 300ml of benzene and 15g of Fe powder are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, stirred and heated to 60 ℃, and reacted for 1 hour to obtain 18g of white product with the content of 99.1 percent.
3. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 6ml of sulfuric acid (93%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 3 ℃, adding 5g of potassium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: 100ml of cyclohexane, 3-methyl-4-hydroxy, was charged in a 500ml three-necked flask equipped with a stirrer and a thermometer13g of benzoic acid, dissolved with stirring at room temperature, Ca (OH) was added26g, stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into a three-necked bottle within 0.5 hour. 25.4g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer were charged the above azo compound, Ca (OH)210g, paraformaldehyde 12g and deionized water 280 ml. Stirring, heating to 50 deg.C, reacting for 1 hr to obtain yellow semi-reduced product 22.9 g.
d, reduction reaction: 23g of semi-reduction product, 300ml of benzene, 10g of Sn powder and 2g of hydrazine are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, and the mixture is stirred and heated to 60 ℃ to react for 1 hour to obtain 19g of white product with the content of 99 percent.
4. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 6ml of hydrochloric acid (93%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to-1 ℃, adding 5.3g of sodium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: 50ml of cyclohexane, 30ml of petroleum ether and 13g of 3-methyl-4-hydroxy-benzoic acid are added into a 500ml three-necked flask equipped with a stirrer and a thermometer, stirred and dissolved at room temperature, KOH5.5g is added, the stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into the three-necked flask within 0.5 hour. 25.2g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer were charged the above azo compound, Ca (OH)29g of NaHS20g and 280ml of deionized water. Stirring, heating to 50 deg.C, reacting for 1 hr to obtain 23.1g yellow semi-reduced product.
d, reduction reaction: 23g of semi-reduced product, 300ml of benzene, 6g of Sn powder and 2g of Zn powder are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, and the mixture is stirred and heated to 60 ℃ to react for 1 hour to obtain 19g of white product with the content of 99.3 percent.
5. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 6ml of hydrochloric acid (93%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 0 ℃, adding 5.3g of sodium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: 50ml of cyclohexane, 30ml of petroleum ether and 13g of 3-methyl-4-hydroxy-benzoic acid are added into a 500ml three-necked flask equipped with a stirrer and a thermometer, stirred and dissolved at room temperature, KOH5.5g is added, the stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into the three-necked flask within 0.5 hour. 25.2g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer were charged the above azo compound, Ca (OH)29g, hydrazine 20g, and deionized water 280 ml. Stirring, heating to 50 deg.C, reacting for 1 hr to obtain 23.1g yellow semi-reduced product.
d, reduction reaction: 23g of semi-reduced product, 300ml of benzene, 6g of Sn powder and 2g of Zn powder are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, and the mixture is stirred and heated to 60 ℃ to react for 1 hour to obtain 19g of white product with the content of 99.3 percent.
6. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 6ml of sulfuric acid (93%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 0 ℃, adding 6g of potassium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: in a 500ml three-necked flask equipped with a stirrer and a thermometer, 13g of cyclohexane 100ml, 3-methyl-4-hydroxy-benzoic acid was charged, and after dissolving by stirring at room temperature, Ca (OH) was added26g, stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into a three-necked bottle within 0.5 hour. 25.4g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer were charged the above azo compound, Ca (OH)210g, paraformaldehyde 12g and deionized water 280 ml. Stirring, heating to 50 deg.C, reacting for 1 hr to obtain yellow semi-reduced product 22.9 g.
d, reduction reaction: 23g of semi-reduction product, 300ml of benzene, 10g of Sn powder and 2g of hydrazine are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, and the mixture is stirred and heated to 60 ℃ to react for 1 hour to obtain 19g of white product with the content of 99 percent.
7. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 6ml of hydrochloric acid (93%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 0 ℃, adding 5.3g of sodium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: 50ml of cyclohexane, 30ml of petroleum ether and 13g of 3-methyl-4-hydroxy-benzoic acid are added into a 500ml three-necked flask equipped with a stirrer and a thermometer, stirred and dissolved at room temperature, KOH5.5g is added, the stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into the three-necked flask within 0.5 hour. 25.2g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer were charged the above azo compound, Ca (OH)29g of NaHS20g and 280ml of deionized water. Stirring, heating to 50 deg.C, reacting for 1 hr to obtain 23.1g yellow semi-reduced product.
d, reduction reaction: 23g of semi-reduced product, 300ml of benzene, 6g of Sn powder and 2g of Zn powder are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, and the mixture is stirred and heated to 60 ℃ to react for 1 hour to obtain 19g of white product with the content of 99.3 percent.
The product synthesis route is as follows:
synthesis of diazonium salt
Synthesis of di-and azo compounds
Synthesis of three, half reduction product
IV, synthesis of reduction product
The absorption principle of benzotriazole ultraviolet absorber
The benzotriazole ultraviolet absorbent can selectively absorb ultraviolet with the wavelength of 290-400nm, and a hydrogen atom on an ortho-hydroxyl and a nitrogen atom on benzotriazole generate a resonance effect. Researches show that the benzotriazole ultraviolet absorbers exist in a phenolic structure, and the light resistance of the benzotriazole ultraviolet absorbers is because the benzotriazole ultraviolet absorbers can perform reversible tautomeric conversion through hydrogen bond chelating rings in molecules, and after ultraviolet light is absorbed, protons can be rapidly transferred to nitrogen atoms to form tautomers, so that excitation energy is effectively converted, and redundant energy is rapidly converted into heat energy to be released, so that the absorbed energy is consumed, and the ultraviolet absorbers return to the ground state. Thus, the ultraviolet energy is converted into heat to be discharged, and the damage of the ultraviolet to the plastic products is avoided.
The synthesis process of the invention is divided into three steps: firstly, synthesizing diazonium salt; secondly, synthesizing an azo compound; and thirdly, reducing the azo compound. Other benzotriazole reductions require two steps (semi-reduction, reduction), thus reducing the synthesis steps.
The ultraviolet blocking rate of the 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole is the highest because the compound contains carboxyl which is an electron-withdrawing group in a benzene ring system, so that the electron cloud density of the whole compound is reduced, and after ultraviolet light is absorbed, carboxyl groups cause faster transfer of hydrogen protons to nitrogen atoms due to electron withdrawing effects to form tautomers, benzotriazole compounds are light-fast because of their reversible tautomeric conversion by intramolecular hydrogen bond chelating rings, while the presence of methoxy groups accelerates the degree of tautomeric conversion of the compounds, therefore, it is understood that 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole has a higher ultraviolet blocking ratio than the other three benzotriazole compounds. Since the hydroxyl group is at the 4-position and cannot undergo proton transfer with the nitrogen atom, the ultraviolet blocking ratio is the best of the four compounds, and this result also proves that the mechanism of ultraviolet absorption by the benzotriazole-based ultraviolet absorber is correct.
As shown in FIG. 1, the absorption range of the ultraviolet light is 200-520 nm, the strongest absorption is 400-500nm, and the absorption intensity is about 80%, so that the ultraviolet light has the advantages of simple synthesis, low cost, good fusion with plastics, long aging resistance time and the like.
Claims (10)
1. A process for the manufacture of 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole comprising the steps of:
a. reacting o-nitroaniline with alkali metal nitrite under the conditions of inorganic strong acid and low temperature to synthesize diazonium salt;
b. under the alkaline condition, 3-methyl-4-hydroxy-benzoic acid is dissolved in aliphatic solvent and coupled with diazonium salt under the low temperature condition to obtain azo compound;
c. the azo compound is used for producing a semi-reduction product under the action of a reducing agent under the alkaline condition;
d. the semi-reduction product is put in organic solvent and under the action of metal reducing agent, so that the product is obtained.
2. The process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the strong inorganic acid used is hydrochloric acid or sulfuric acid.
3. The process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the reaction temperature in the a.b step is controlled below 5 ℃.
4. The process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the alkali metal nitrite used includes sodium nitrite or potassium nitrite.
5. According to the rightThe process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the alkaline condition is that a certain amount of NaOH, KOH or Ca (OH) is added into a solvent2And (4) forming.
6. The process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the aliphatic solvent comprises cyclohexane, octane and petroleum ether.
7. The process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the reducing agent comprises inorganic salts: na (Na)2S、NaHS、NH4HS、(NH4)2S and their mixture, the aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, paraldehyde, reducing sugar, and hydrazine.
8. The process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the metal reducing agent comprises Zn, Sn, Al, Fe and a mixture thereof.
9. The process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the organic solvent comprises dimethylbenzene, methylbenzene and benzene.
10. The process for producing 2- (2 ' -hydroxy-3 ' -methyl-5 ' -carboxyphenyl) benzotriazole according to claim 1 wherein: the molar ratio of the o-nitroaniline to the 3-methyl-4-hydroxy-benzoic acid is 1: 1; the mass ratio of the alkali metal nitrite to the o-nitroaniline is 5-6: 10.
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| US3214436A (en) * | 1960-12-19 | 1965-10-26 | American Cyanamid Co | Benzotriazole compounds |
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| CN110066252A (en) * | 2019-05-29 | 2019-07-30 | 襄阳金达成精细化工有限公司 | A kind of preparation method of ultraviolet absorbing agent UV-329 |
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| US3214436A (en) * | 1960-12-19 | 1965-10-26 | American Cyanamid Co | Benzotriazole compounds |
| US5071995A (en) * | 1988-10-07 | 1991-12-10 | Kuraray Co., Ltd. | 2-hydroxyphenylbenzotriazol compounds and the use thereof |
| JPH03200788A (en) * | 1989-12-27 | 1991-09-02 | Kuraray Co Ltd | Benzotriazole-based compound and use thereof |
| CN102295613A (en) * | 2010-06-25 | 2011-12-28 | 吉林师范大学 | Method for preparing 2-(2'-hydroxyl 5'-tert-octyl phenyl)benzotriazole |
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